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Hydroaminomethylation of olefins

a technology of olefins and methylated olefins, which is applied in the field of phosphite ligands less suitable for the desired reaction, poor amine selectivity, and no conversion

Active Publication Date: 2005-09-29
UNION CARBIDE CORP
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The researchers also tested a monodentate phosphite ligand under the same reaction conditions but discovered poor amine selectivity—and no conversion to the desired linear amine—from which they concluded that “phosphite ligands are less suitable for the desired reaction because of hydrolysis problems encountered in the presence of water and amines.” Id. at 1677.
Also, long reaction times require extended use of process equipment, which result in increased processing costs.

Method used

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  • Hydroaminomethylation of olefins

Examples

Experimental program
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Effect test

example 1

Preparation of Dimethylaminomethylalkane mixture

[0022]

[0023] Neodene® Olefin Blend (10 / 1112 / 13 / 12, 319 g, obtained from Shell Chemical) olefin substrate was added to a 1-gal (4-L) reactor in THF (680 g). To this solution was added dimethylamine (222 g), and a solution of a complex prepared from [Rh(CO)2(acac)] (3.7 g) and tris(2,4-di-t-butylphenyl)phosphite (46.2 g, obtained from Aldrich Chemical) in THF (374 g). The final rhodium concentration was about 900 ppm by weight. This mixture was heated to 80° C. and pressurized to 600 psi (4140 kPa) with syngas and stirred under these conditions for 7 hours. The reactor was cooled to 21° C. overnight and the gas phase vented. After stirring under a nitrogen flow for about 1 hour to remove most of the excess dimethylamine, the reactor contents were dumped, stripped of THF and distilled using a Kugelrohr apparatus to yield a colorless mobile liquid (427 g, 99% yield).

example 2

Hydroaminomethylation of Oleic Acid Diethanolamide with Diethanolamine

[0024]

[0025] Oleic acid amide (13.49 g), diethanolamine (4.51 g) and THF solvent (20 mL) were added to a nitrogen purged reactor by syringe. The reactor was stirred under ca. 200 psi (1380 kPa) of syngas to saturate the solution. After venting, an aliquot (10.4 g) of a pre-made catalyst solution of [Rh(CO)2(acac)] (5351 ppm by weight Rh) and tris(2,4-di-t-butylphenyl)phosphite ligand (5.00 moles of ligand / mole of Rh) in THF was added to the reactor. The reactor was sealed and pressurized with syngas and heated to 80° C. The pressure was increased to 600 psi (4140 kPa) with additional syngas, and then fed on demand at this pressure throughout the reaction. After 4.5 hours, the reactor was cooled, vented and the reactor contents discharged. The amber solution was extracted with cyclohexane, then toluene, and the supernatent discarded. Acetonitrile was added to the lower brown layer, and stirred briefly. When agitat...

example 3

Hydroaminomethylation of Terminally Unsaturated Isopolypropylene with Dibenzylamine

[0026]

[0027] Vinylidene-terminated polypropylene having a weight average molecular weight Mw of about 1800 g / mol (5.43 g, obtained from Baker-Hughes Corporation) was dissolved in toluene (70 mL). A portion of this solution (65 mL) was transferred to a 100 mL Parr reactor, whereupon dibenzylamine (2 mL, 9.8 mmols) and a solution containing complex (20 mL of a stock solution prepared by dissolving [Rh(CO)2(acac)] (2.56 g), 2,4-di-t-butylphenylphosphite (32.09 g), in sufficient THF to give a total solution mass of 200.73 g) was added. The reactor was sealed and pressurized to 600 psi (4140 kPa) of syngas and heated to 80° C. for 130 minutes. After reaction, the pressure was released and the reactor opened while the temperature was still at 60° C., and the contents discharged into a glass beaker. The polymer product was precipitated by addition of methanol (about 2× volume). The solid material was filter...

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Abstract

The present invention relates to a method comprising the step of contacting under hydroaminomethylation conditions, an olefin, an amine, a rhodium-phosphorous ligand, and synthesis gas (syngas). In particular, it has been discovered that, under some circumstances, a neutral rhodium-monodentate phosphite ligand is prescribed. The invention provides a simple way of making, in high yields and regiospecificity, a variety of products, including pharmacologically active products such as ibutilide, terfenadine, and fexofenadine, and derivatives thereof.

Description

BACKGROUND OF THE INVENTION [0001] The present invention relates to hydroaminomethylation of olefins. Aliphatic amines are useful in a variety of applications including agrochemical and pharmaceutical products and intermediates, as well as precursors for polymers such as polyurethanes. The homogeneous hydroaminomethylation reaction was reported by Reppe at BASF (Liebigs Ann. Chem. 1953, 582, 133-161) using a homogeneous cobalt carbonyl catalyst. This reaction consists of a tandem, one-pot olefin hydroformylation / reductive amination sequence in which the intermediate aldehyde reacts with a primary or secondary amine to form an imine or enamine intermediate, which undergoes hydrogenation to form a secondary or tertiary amine. U.S. Pat. No. 3,513,200 reports the use of a homogeneous rhodium triphenylphosphine catalyst for synthesis of tertiary amines via hydroaminomethylation. The use of hydroaminomethylation with ethylene to form n-propylamines was reported by Jones in J. Organomet. C...

Claims

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Application Information

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Patent Type & Authority Applications(United States)
IPC IPC(8): C07C29/60C07C33/30C07C69/732C07C209/26C07C209/60C07C211/03C07C211/17C07C231/12C07C237/08C07C311/08C07D211/22C07D215/22C07D215/227C07D295/023
CPCC07C33/30C07C69/732C07C209/60C07C231/12C07C311/08C07D211/22C07D295/023C07D215/227C07C211/17C07C237/08
Inventor BRIGGS, JOHN R.WHITEKER, GREGORY T.KLOSIN, JERZY
Owner UNION CARBIDE CORP
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